Process for the manufacture of coloured polycyclic metal complexes

ABSTRACT

WHEREIN A1 and A2 are carbocyclic or heterocyclic aromatic radicals, R1 and R3 are hydrogen atoms, aliphatic hydrocarbon radicals or aryl radicals, and R2 is a hydrogen or halogen atom or an alkyl, aryl, nitro, nitrile or arylazo group, chargerised in that a carbocyclic or heterocyclic aromatic 1,2-diamine is reacted with a 1,3-dicarbonyl compound in the presence of a divalent metal ion, in an organic solvent. The products obtained according to this process a valuable pigments for coloring plastics.   Process for the manufacture of polycyclic metal complexes of the formulae

United States Patent [191 LEplattenier et al.

[45] Apr. 15, 1975 PROCESS FOR THE MANUFACTURE OF COLOURED POLYCYCLICMETAL COMPLEXES [75] Inventors: Francois LEplattenier, Thcrwil;

Andre Pugin, Riehen, both of Switzerland [73] Assignee: Ciba-GeigyCorporation, Ardsley,

[22] Filed: Dec. 12, 1972 [21] Appl. No.: 314,492

[30] Foreign Application Priority Data Dec. I5, I97! Switzerlandl8356/7l [52] US. Cl. 260/146 R; 106/208 Q; 260/37 P;

260/145 C; 260/239 BC; 260/270 R [51] Int. Cl.. C09b 45/28; C09b 45/30;C09b 45/32 [58] Field of Search 260/145 C, 146 R [56] References CitedFOREIGN PATENTS OR APPLICATIONS 369,837 7/1963 Switzerland 260/146 ROTHER PUBLICATIONS Dimroth et al., 5.l4-Dihydro-Dibenzo[b,l][5.9.l4.- l8]tetraaza[ l4]Annulen, Ein Makrocyclischer Chelat- Annalen, 717, 1968.

Primary ExaminerFloyd D. I-Iigel Assistant ExaminerC. F. WarrenAttorney, Agent, or FirmVincent J. Cavalieri [57] ABSTRACT Process forthe manufacture of polycyclic metal complexes of the formulae Theproducts obtained according to this process a valuable pigments forcoloring plastics.

4 Claims, No Drawings PROCESS FOR THE MANUFACTURE OF phenylenediamine,4-cyano-l,Z-phenylenediamine, 4- COLOURED POLYCYCLIC METAL COMPLEXESacetylamino-LZ-phenylenediamine, 4-benzoylamino- It has been found thatvaluable, coloured polycyclic LLphenylenediamine, 3,4-diaminodiphenyl.1.2- metal Complexes Of the formulae diaminonaphthalene.2,3-diaminonaphthalene. 1.2-

5 1 F II C R c-- R u I g f 3 A A 2 C C l i \N I II R c-- R R l 3 1 C C Rwherein A and A denote carbocyclic or heterocyelic diamino-S.6.78-tetrahydronaphthalene. 2.3-diaminoaromatic radicals Me denotes adivalent metal atom. 6,7,8-tetmhydronaphthalene. 1.2- n a denote y g natoms r lkyl r ryl r idiaminoanthraquinone, 2.3-diaminoanthraquinone.cals which are optionally substituted, for example by9.10-diaminophenanthrene. 5.6- hlllogefi atoms, n tes a hydrogen orhalogen atom diaminoacenaphthene. 3,4-diaminopyridine. 2.3- or an alkyl,aryl. nitro. nitrile or arylazo gr up r th diaminodiphenylene oxide.2.3-diaminoquinoxaline. radicals R and R together form a fusedcarbocyclic d 2 h 1 5 6 di mino-benzimidazol. ring, are obtained if acarbocyclic or heterocyclic aro- P ibl 1 3 di -b 1 compounds wt i i mimell'diilmiml is reacted with u y lar. 1,3-dialdehydes or 1,3-diketones ofthe formula compound in the presence ofa divalent metal ion in anorganic solvent.

Aromatic 1,2-diamines used are preferably 0- 2 phenylenediamines,especially those of the formula I 0 IMCOCHCOR 2 wherein R and R denotehydrogen atoms or optionally substituted alkyl or aryl groups and Rdenotes a hydrogen or halogen atom or an alkyl, aryl. nitro, III cyanoor arylazo group, especially an optionally substi- Z tuted hen l' ftheformula Y p y azo group 0 wherein X and Y denote hydrogen or halogenatoms or 1 alkyl, alkoxy, phenoxy, phenyl, alkylsulphonyl, carboxy,alkoxycarbonyl, acylamino, aminocarbonyl or N: sulphonic acid groups, ortwo adjacent radicals X and V Y together form a fused carbocyclic orheterocyclic 5- Y membered or 6-membered ring. As examples there may bementioned: 12- 1 phenylenediamine, 4-chloro-l ,2-phenylenediamine,4,5-dichloro-l .Z-phenylenediamine, 4-methyl-l,2- wherein X, and Ydenote hydrogen or halogen atoms phenylenediamine, 4,5-dimethyl-l,2- oralkyl, alkoxy, phenoxy, phenylazo, acyl, aminocarphenylenediamine,3,5-dimethyl-l ,2- bonyl, trifluoromethyl, alkylsulphonyl,alkoxycarbonyl, phenylenediamine, 4-methoxy-l,Z-phenylenediamine,acylamino, for example alkanoylamino or ben-4-phenoxy-LZ-phenylenediamine. 4-methylsulphonylzoylamino, nitro, cyano,carboxylic acid or sulphonic l.2-phenylenediamine, 4-ethylsulphonyl-l,2- acid groups and Z, denotes a hydrogen or halogen atomphenylenediamine, 4-carboxy-l,Z-phenylenediamine, or an alkyl group.4-methoxycarbonyl-l,Z-phenylenediamine, 4- As examples there may bementioned: malondialdeethoxycarbonyl-l,2-phenylenediamine, hyde,2-chlor0malondialdehyde, 2- butoxycarbonyl'l l-p y fimethylmalondialdehyde, Z-cyanomalondialdehyde, xyl xy r nyll .2-ph nyleni min phenyl-azo-malondialdehyde, 4'-chloro-phenyloctyloxycarbonyl-l.2-phenylenediamine, 4-nitrol .2- azomalondialdehyde,2,4'-dichloro-phenyl-azo- 2,5-dichloro-phenyl-azo- 2 ',4 ',5'-trichlorophenyl-azo- 4-nitro-phenyl-azo- 4-cyano-phenyl-azo-4-methylsulphonyl-phenyl-azo- 3'-acetylamino-phenyl-azo-2-sulpho-phenyl-azo- 3'-sulpho-phenyl-azo- 3'-carboxy-phenyl-azoareparticularly preferentially used as metal com-' pounds. These metals areappropriately employed in the form of their soluble salts. for exampletheir chlorides or sulphates. or especially in the form of the salts ofthe lower fatty acids. for example of acetic acid. pro pionic acid orbutyric acid.

The reaction appropriately takes place in a hydrophilic organic solvent,for example in a lower aliphatic alcohol, such as methanol, ethanol,propanol. isopropanol. butanol or isobutanol. ethylene glycolmonomethylether or ethyl ether, or in a lower fatty acid, especially acetic acid,at temperatures between 50 120C, especially 60 90C.

Depending on the choice of the solvent or of the dicarbonyl compound,the tricyclic compounds of the Formula 1 or the tetracyclic compounds ofthe Formula 11 are obtained. The tricyclic compounds are probablyintermediate products for the tetracyclic compounds. lf, now, the natureand amount of the solvent are so chosen that the tricyclic compounds aresparingly soluble therein, these precipitate from the reaction mixturebefore a further reaction to give the tetracyclic compound occurs. Evenif all the radicals R R and R of the dioxo compound are different fromhydrogen, the reaction stops at the tricyclic compounds, presumably forsteric reasons.

By virture of their insolubility in the reaction medium. the metalcomplexes obtained can easily be isolated by filtration. They arevaluable dyestuffs which can be used for dyeing the most diversematerials. The compounds which are free of acid groups which confersolubility in water are in particular suitable for pigmenting highmolecular organic material, for example cellulose ethers and celluloseesters, such as cthylcellulose. acetylcellulose or nitrocellulose,polyamides, polyurethanes or polyesters, natural resins or syntheticresins. for example aminoplasts, especially ureaformaldehyde andmelamine-formaldehyde resins, alkyd resins. phenoplasts, polycarbonates.polyolefines, such as polystyrene, polyvinyl chloride, polyethylene,polypropylene. polyacrylonitrile, polyacrylic acid esters, rubber,casein, silicone and silicone resins, individually or as mixtures. Hereit does not matter whether the high molecular compounds mentioned are inthe form of 4-sulpho-phenyl-azoplastic masses or melts or in the form ofspinning solutions. lacquers. paints or printing inks. Depending on theend use, it proves advantageous to use the new pigments as toners or inthe form of preparations. The new pigments are as a rule distinguishedby high general fastness properties, colour strength and fastness tomigration.

Those of the compounds obtained according to the invention which containsulphonic acid groups can be converted by reaction with water-solublecalcium salts or barium salts into the insoluble calcium lakes or bariumlakes, which are also outstandingly suitable for use as pigments.

Those metal complexes of the Formulae 1 and 11 wherein R denotes ahalogen atom or a nitro, nitrile or arylazo group are new compounds.

The success of the process according to the invention is surprisingsince it is known from the literature that o-diamines react with1,3-dicarbonyl compounds to give 1,5-diazepines. (See, for example, F.D.Popp and A. Catala Noble: The Chemistry of Diazepines" in Advances onHeterocyclic Chemistry 8 21-82, especially page 67-68, (1967). andJager. Z. anorg. und allg. Chemie 364 180 (1969)). Admittedly, tricyclicand tetracyclic metal complexes of the Formulae 1 and 11 in which R: ishydrogen are already known. They result. for example. from the reactionof o-diamines with ethinyl compounds. such as propargylaldehyde. in thepresence of metal-donating agents (see DOS 1.569.667 which was publishedon Jan. 14. 1971 and Dimroth. Annalen 717, 137 (1968)). However. it isnot possible by means of this process to arrive at compounds of theFormula 1 wherein R is different from hydrogen; furthermore, the ethinylcompounds which serve as the starting substances are more difficult toobtain than the 1,3-dicarbonyl compounds to be used according to theinvention. It is furthermore known that compounds of the Formula 1 areobtained if 2 mols of a 2- alkoxymethylene-l,3-dicarbonyl compound areallowed to react with 1 mol of an o-phenylenediamine and the reactionproduct is subsequently metallised. In a second stage, the metalcomplexes of the Formula 1 can be cyclised in a melt ofo-phenylenediamine to give the tetracyclic compounds of the Formula 11[see Jager.

starting products which are simply accessible and permits greatervariation of the substituent R According to Jager, Z. anorg. and allg.Chemie 337 page 84. compounds of the Formula 1 can furthermore bemanufactured by reacting 2 mols of the sodium salt of an appropriatehydroxymethyleneketone with 1 mol of a l,2-diamine, for example ofo-phenylenediamine, and subsequently metallising the compound formed. Inthis case, however, in contrast to the use of free 1,3- dicarbonylcompounds, a diazepine formation is not possible as a competingreaction.

In the examples which follow the parts, unless other wise stated, denoteparts by weight and the percentages denote percentages by weight.

EXAMPLE 1 5.28 g (0.030 mol) of phenylazomalondialdehyde are added at60C to a solution of 3.72 g (0.015 mol) of Ni(CH,,COO) 4 H 0 and 3.24 g(0.030 mol) of o- 3 ,8 78,188 5 6 phenylenediamine in 100 ml of glacialacetic acid. The reaction mixture is stirred for 5 minutes at the refluxtemperature. whereupon a brown precipitate forms (Molecular weight 5517)after a few seconds. After cooling to C. the mixture and acetone. 8.80 g(88% of theory) of the analytically pure dyestuff of the formula isfiltered and the residue is washed with glacial acetic 5 galculued C H NNi d acid. water and acetone. 5.8 g of theory) of the mm 6; 1 W m4 browndyestuff of the formula 1' 1-N m Hi] TH EXAMPLE 2 15 N N 4.90 g (0.020mol) of 2.5-dichlorophenyl-azomalo-ndialdehyde are added at 60C to asolution of Ni 2.49 g (0.010 mol) of Ni(CH;;COO) .4H O and 5.28 g (0.020mol) of 3.4-diaminobenzoic acid 2-octy1 ester in N N 20 ml of glacialacetic acid. The reaction mixture is 1 I stirred for 5 minutes at thereflux temperature where- CH VI upon a red-brown precipitate forms aftera few seconds. After cooling to 20C the mixture is filtered off 01 uc cu3 CW 0 11 L i) ((111 and the residue is washed with glacial acetic acid.water 55 which dyes polyvinyl chloride in brown shades, are obwhich dyespolyvinyl chloride is brown shades. are obtained. tained.

Analysis: C ,.H CI N NiO (Molecular weight 1002.7)

Calculated C 57.4 H 498 C1 14.15 N 11.15 Ni 5.85 Found 573 5.1 14.3 11.35.9

EXAMPLE 3 c c l l N N VIII which dyes polyvinyl chloride in greenshades, are obtained.

Analysis:

Calcu- C 65.9 H 5.93 N l3.97 Ni 14.64 lated Found 64.5 5.4 13.8 NS

The table which follows lists further tetracyclic metal complexes of theinitially mentioned Formula I), which were obtained if, following theinstructions of the prel5 ceding examples, a dioxo compound of theformula R COCHCOR 5 wherein the substituents R R and R have the meaningsindicated in columns 2-4, is reacted with the 1,2- diamine mentioned incolumn 5 and the acetate of the metal listed in column 1. The dyestuffsobtained dye polyvinyl chloride in brown shades. with the exception 3 CHH 30 of Examples 26 and 27. which dye PVC in green 3 shades.

Metal R R R 1,2-Diamine 4 Ni H H H o-Phenylenediamine 5 N1 H CH Ho-Phenylenediamine 6 Ni H H CH o-Phenylenediamine 7 Ni H CN Ho-Phenylenediamine 8 Ni H CH H 4-Phenoxy-l,Z-phenylenediamine 9 Ni HPhenylazo H o-Phenylenediamine 10 Ni H Phenylazo H 4-Ch1oro-l,Z-henylenedian ine 11 Ni H Phenylazo H 4,5-Dichloro-1,2-phenylenediamine12 'Ni H Phenylazo H 4-Ethylsu1phonyl-l,2-phenylenediamine 13 Ni HPhenylazo H 2,3-Diamino-quinoxaline Continued 14- Ni H Phenylazo H2,5-Diaminodiphenylene oxide 15 Ni H P-Chlorophenylazo Ho-Phenylenediamine 16 Ni H p-Chlorophenylazo H 4-Carboxy-l,2-phenylenediamine 17 Ni H p-Nitrophenylazo H o-Phenylenediamine 18 N1H o-Sulphophnylazo H o-Phenylenediamine 19 Ni H m-Acetylaminophenylazo Ho-Phenylenediamine 20 Ni H p-Cyanophenylazo H o-Phenylenediamine 21 Ni H2' ,5'-Disulphophenylazo H o-Phenylenediamine 22 Ni H 2,5'-Dichlorophenylazo H o-Phenylenediamine N1 H 2' ,5'-DichlorophenylazoH 3,4-Diaminobenzoic acid 2 '-noctyl ester 24- Ni H 2' ,4 ,5'-Tr1chlorophenylazo H o-Phenylenediamine 25 N1 H 2' ,3,4'-Trich1oropheny1azo H o-Phenylenediamine 26 Ni CH H CH 4,5-Dimethyl-l,Z-phenylenediamine 27 Ni CH H CH 4-Chloro-l ,2-phenylenedia.mine

28 Ni H p-Acetylphenylazo H o-Phenylenediamine 29 Ni H p-AcetylphenylazoH 2,3-Diaminopyridine 30 Ni H p-Cyanophenylazo H 2 ,3-Diaminopyridine 31Ni H Phenylazo H 2,5-Diamdnopyridine 32 Ni H p-Phenylazo-phenylazo Ho-Phenylenediamine 33 N1 H p-Acetylamino-phenylazo H o-Phenylenediamine34 Ni H Phenylazo H 4-Nitro-l,Z-phepylenediamine I 55 Cu H Phenylazo HO-PHenylenediamine 36 Cu H p-Cyanophenylazo H o-Phenylenediamine 37 Cu H'p-chlorophenylazo H 'o-Phenylenediamine 38 Zn H Phenylazo I I Ho-Phenylenediamine 59 Ni H Phenylazo H *2 c1 mapwouu- -c1 40 Cu H dittoH ditto 41 Ni H p-Acetylphenylazo H ditto 42 Cu H ditto H ditto 43 Ni HPhenylazo H H N CH O H NnCONH- C1 OCH Continued 44 Cu ditto H ditto 45Ni p-Acetylphenylazo H ditto 46 Cu H 'p-Acetylphenflazo" H l-l N CH H NCONH- OCl-1 47 'Co H Phenylazo" H N C1 48 Co B p-acetylphenylazo HEXAMPLE 49 EXAMPLE 50 A solution of 12.44 g (0.05 mol) ofNi(CH COO) .4-H and of 5.40 g (0.05 mol) of o-phenylenediamine in 400 ml ofmethylcellosolve in warmed to 80C under nitrogen over the course of 1hour. 22.0 g (0.10 mol) of p-nitro-phenylazomalondialdehyde dissolved in400 ml of methylcellosolve are then added dropwise and the reactionmixture is stirred for a further 2 hours at 80C (under nitrogen). Aftercooling to C, the dyestuff which has precipitated is filtered off andwashed with methylcellosolve, water, alcohol and acetone. 15.7 g (55% oftheory) of the dark brown nickel complex of the formula are obtained.

65 parts of stabilised polyvinyl chloride. 35 parts of dioctyl phthalateand 0.2 part of the dyestuff obtained according to Example 1 are stirredtogether and then milled on a two-roll calender for 7 minutes at C. Afilm which is dyed brown, of good fastness to light and migration, isobtained.

We claim:

1. A polycyclic metal complex of the formula wherein X and Y ishydrogen, chloro, lower alkyl, lower alkoxy. phenoxy. phenyl, carboxy,lower alkoxycarbonyl. lower alkanoyl amino, aminocarbonyl, loweralkylsulphonyl or sulphonic acid group; Me is Cu,Zn,Ni or C0; X and Y,are hydrogen, chloro, lower alkyl, lower alkoxy. phenoxy. phenylazo,loweracyl, trifluoromethyl. lower alkylsulphonyl, nitro, cyano,alkoxycarbonyl. acetylamino. aminocarbonyl, carboxylic acid group orsulphonic acid group; and Z is hydrogen, chloro, or acetyl.

4. The polycyclic metal complex of claim 1 of the formula 2. Thepolycyclic metal complex of claim 1 of the formula 3. The polycyclicmetal complex ofcluim l of the formula

1. A POLYCYCLIC METAL COMPLEX OF THE FORMULA
 2. The polycyclic metalcomplex of claim 1 of the formula
 3. The polycyclic metal complex ofclaim 1 of the formula
 4. The polycyclic metal complex of claim 1 of theformula